[go: up one dir, main page]

US20040197483A1 - Method of manufacturing carbonate film, carbonate composite material, and method of manufacturing the same - Google Patents

Method of manufacturing carbonate film, carbonate composite material, and method of manufacturing the same Download PDF

Info

Publication number
US20040197483A1
US20040197483A1 US10/817,839 US81783904A US2004197483A1 US 20040197483 A1 US20040197483 A1 US 20040197483A1 US 81783904 A US81783904 A US 81783904A US 2004197483 A1 US2004197483 A1 US 2004197483A1
Authority
US
United States
Prior art keywords
carbonate
group
organic matrix
manufacturing
acid group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US10/817,839
Other versions
US7198825B2 (en
Inventor
Hiroaki Wakayama
Yoshiaki Fukushima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Central R&D Labs Inc
Original Assignee
Toyota Central R&D Labs Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Central R&D Labs Inc filed Critical Toyota Central R&D Labs Inc
Assigned to KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO reassignment KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WAKAYAMA, HIROAKI, FUKUSHIMA, YOSHIAKI
Publication of US20040197483A1 publication Critical patent/US20040197483A1/en
Application granted granted Critical
Publication of US7198825B2 publication Critical patent/US7198825B2/en
Adjusted expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/26—Carbonates
    • C04B14/28—Carbonates of calcium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials

Definitions

  • the present invention relates to a method of manufacturing carbonate film capable of manufacturing in a short time, a carbonate composite material excellent in strength, and a method of manufacturing the same.
  • Crystals of carbonate such as calcium carbonate have an excellent strength, and are highly expected as high strength material. Further, when combined with wood or other conventional material, carbonate is expected to be used as a composite material excellent in strength.
  • a pearl layer structure of seashell having unique gloss and sufficient strength is known.
  • calcium carbonate crystals of uniform thickness of 1 ⁇ m or less form a regular layer structure together with biological polymer.
  • the pearl layer structure of seashell has an excellent strength.
  • the present invention has been made in consideration of such conventional problems, and an object of the present invention is to provide a method of manufacturing carbonate film capable of manufacturing a large area of carbonate film in a short time, a carbonate composite material excellent in strength, and a method of manufacturing the same.
  • a first aspect of the present invention relates to a method of manufacturing carbonate film comprising the steps of:
  • a pressure container with a base material having at least part of the surface coated with an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and a material solution containing a carbonate material as a material for carbonate film and an organic polymer including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and
  • the base material having at least a part covered with the organic matrix, and the material solution containing carbonate material and organic polymer are processed in the pressure container in the presence of CO 2 at 2 atm or higher.
  • the carbonate film is estimated to be formed in the following process.
  • At least one member possessed by the organic matrix selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group mutually act with part of one or more functional groups possessed by the organic polymer selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and at least part of the organic polymer is adsorbed on the surface of the base material.
  • the carbonate film After forming the carbonate film, the carbonate film can be peeled from the base material and used.
  • the carbonate film is formed in the presence of CO 2 at 2 atm or higher. Accordingly, the solubility of CO 2 dissolved in the material solution is enhanced. As a result, the carbonate film is deposited quickly and the carbonate film can be manufactured promptly. Since the deposition amount of carbonate is large, a carbonate film of a large area can be manufactured.
  • the method of manufacturing the first aspect of the present invention uses CO 2 which is inexpensive, nontoxic, and incombustible. Therefore, the carbonate film can be manufactured at low cost and with high safety.
  • the first aspect of the present invention it is available to provide a method of manufacturing carbonate film capable of manufacturing a large area of carbonate film in a short time.
  • a carbonate composite material comprises crystals of carbonate, and an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, wherein the crystals of carbonate are disposed on the surface and/or in pores of the organic matrix.
  • the carbonate composite material is composed of crystals of the carbonate, and the organic matrix such as wood having a plurality of fine pores on the surface and/or in the inside, and crystals of the carbonate are disposed on the surface and/or in the pores of the organic matrix. Since the crystals of carbonate are very high in strength, the carbonate composite material is very high in strength as compared with the organic matrix alone.
  • a method of manufacturing carbonate composite material having crystals of carbonate on the surface and/or in pores of an organic matrix, comprises the steps of:
  • a pressure container filling a pressure container with an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and a material solution containing a carbonate material, and
  • the organic matrix and the material solution containing carbonate material are processed in the pressure container in the presence of CO 2 at 2 atm or higher.
  • the carbonate excellent in strength is deposited on the surface and/or in the pores of the organic matrix.
  • a carbonate composite material excellent in strength as compared with the organic matrix can be obtained.
  • At least one member possessed by the organic matrix selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group act to localize cations such as calcium ions and/or anions such as carbonic acid ions or hydrocarbon ions contained in the carbonate material at high concentration near the surface of the organic matrix and/or in the pores. As a result, crystals are nucleated, crystals of carbonate grow, and carbonate is deposited.
  • the carbonate is deposited in the presence of CO 2 at 2 atm or higher. Accordingly, the solubility of CO 2 dissolved in the material solution is enhanced. As a result, the carbonate is deposited quickly and the carbonate is deposited promptly on the surface and/or in the pores of the organic matrix. Since the deposition amount of carbonate is large, crystals of carbonate are deposited sufficiently on the surface and/or in the pores of the organic matrix.
  • the method of manufacturing the third aspect of the present invention uses CO 2 which is inexpensive, nontoxic, and incombustible. Therefore the carbonate composite material can be manufactured at low cost and with high safety.
  • the third aspect of the present invention provides a method of manufacturing carbonate composite material excellent in strength.
  • FIG. 1 is an explanatory diagram showing a base material of which upper surface is covered with an organic matrix in embodiment 1 or 2.
  • FIG. 2 is an explanatory diagram showing a carbonate film formed on the surface of organic matrix for covering the base material in embodiment 1 or 2.
  • FIG. 3 is an explanatory diagram showing a plurality of layers of carbonate film laminated on the surface of organic matrix for covering the base material in embodiment 2.
  • FIG. 4 is an explanatory diagram showing a general appearance of carbonate composite material in embodiment 3.
  • FIG. 5 is a sectional view taken in the direction of the arrows substantially along line A-A in FIG. 4.
  • FIG. 6 is a magnified view of pores having carbonate in carbonate composite material in embodiment 3.
  • the base material for example, glass, other ceramics, plastics, metal or wood may be used.
  • organic polymer examples include polyacrylic acid, polyglutamic acid, polyaspartic acid, polyimide, protein, amino acid and derivatives thereof, and related substances.
  • CO 2 is supplied into the pressure container at 2 atm or higher.
  • CO 2 can be introduced into the pressure container in a state of supercritical fluid.
  • the supercritical fluid refers to a fluid existing at temperature and pressure above the critical point of an ordinary substance.
  • the fluid in this state is a substance having a dissolving ability equivalent to that of liquid, and diffusibility and viscosity similar to those of gas.
  • the organic matrix include aspartic acid, cellulose, chitin, chitosan, wood, polyimide, polyacrylic acid, polyvinyl alcohol, and the like.
  • the organic matrix may be modified with a proper functional group.
  • either solid or gel may be used as the organic matrix.
  • the portion of water of the gel can be replaced with the carbonate.
  • a carbonate composite material of complicated shape can be manufactured.
  • the solvent of the material solution for example, water, alcohol, fused salt or ionic solution, polar organic solvent or the like may be used.
  • the carbonate material contain at least one member selected from the group consisting of Ca, Mg, Fe, Cu, Co, Mn, and Ni.
  • the carbonate material contain at least one member selected from the group consisting of carboxylate, carbonate, alkoxide, oxide, hydroxide, chloride, nitrate, acetyl acetonate and derivatives thereof.
  • the method of manufacturing carbonate film in the embodiment, as shown in FIG. 1 and FIG. 2, is characterized by filling a pressure container with a base material 1 having at least part of the surface coated with an organic matrix 2 including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and a material solution containing a carbonate material as a material for carbonate film 3 , and an organic polymer including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group.
  • an organic matrix 2 including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl
  • a slide glass was prepared as the base material 1 coated with a cellulose film as the organic matrix 2 .
  • 10 g of Cu(OH) 2 was dissolved in 100 mL of 25 wt. % NH 3 aqueous solution, and 0.3 g of cellulose powder (Nacalai Tesque, Inc.) was added to 30 mL of its supernatant, and a cellulose solution was prepared.
  • the slide glass (27 mm ⁇ 48 mm) was adhered to a spin coat rotor by a double-side adhesive tape, and the cellulose solution was dropped by dropping pipette, and the rotor was rotated at 390 rpm for 60 seconds to perform spin coating operation.
  • the base material 1 (slide glass) having the upper surface coated with cellulose film as the organic matrix 2 was obtained.
  • a calcium carbonate film was fabricated as carbonate film.
  • the organic polymer 0.024 g of polyacrylic acid (molecular weight: 103) was dissolved in 100 mL of ion exchanged water.
  • CO 2 was supplied in a state of supercritical fluid (30 MPa (300 atm), 90° C.), and held for 1 hour in the condition of 90° C. and 30 MPa (300 atm).
  • a calcium carbonate film was formed as carbonate film 3 .
  • the carbonate film 3 was formed on the organic matrix 2 formed on the upper surface of the substrate 1 .
  • the carbonate film 3 was a uniform film with a thickness of 0.6 ⁇ m.
  • the carbonate was deposited in the presence of CO 2 in a state of supercritical fluid (30 MPa (300 atm), 90° C.).
  • This embodiment is an example of manufacturing multiple layers by laminating a plurality of layers of carbonate film.
  • a base material 1 silica glass having the upper surface coated with an organic matrix 2 was prepared, and a calcium carbonate film with a thickness of 0.6 ⁇ m was formed as carbonate film 3 on the organic matrix 2 of the base material 1 .
  • the organic matrix 2 was formed on the upper surface of the base material 1 same as in embodiment 1, and the carbonate film 3 is formed on the organic matrix 2 .
  • sample 1 was obtained.
  • each carbonate film 3 was laminated in four layers on the organic matrix 2 formed on the upper surface of the substrate 1 .
  • the thickness of each carbonate film 3 was 0.6 ⁇ m, and the thickness was uniform.
  • This embodiment is an example of manufacturing a carbonate composite material composed of crystals of carbonate and the organic matrix.
  • the carbonate composite material 5 of the embodiment is a carbonate composite material composed of crystals of carbonate 55 , and an organic matrix 51 including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group.
  • the crystals of the carbonate 55 are disposed on the surface and in pores 53 of the organic matrix 51 .
  • FIG. 6 is a magnified view of pores 53 of the carbonate composite material 5 shown in FIG. 5.
  • the carbonate composite material 5 of the embodiment is cylindrical white lumps as shown in FIG. 4 and FIG. 5.
  • the white lumps of carbonate composite material 5 are composed of crystals of calcium carbonate as carbonate 55 and carboxymethyl cellulose Na (CMC-Na) in gel form as the organic matrix 51 .
  • crystals of the carbonate 55 cover the surface of the organic matrix 51 , and are disposed in the pores 53 of the organic matrix 51 .
  • the carbonate composite material 5 is higher in strength as compared with the organic matrix 51 alone.
  • the method of manufacturing the embodiment manufactures a carbonate composite material 5 having crystals of carbonate 55 on the surface and/or in the pores 53 of the organic matrix 51 .
  • a pressure container is filled with an organic matrix 51 including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and a material solution containing a carbonate material.
  • the glass cylindrical container was placed in an autoclave with a capacity of 1000 mL, and CO 2 was supplied into the autoclave in a state of supercritical fluid (90° C., 30 MPa (300 atm)), and held for 1 hour in the condition of 90° C. and 30 MPa.
  • supercritical fluid 90° C., 30 MPa (300 atm)
  • crystals of carbonate 55 excellent in strength are applied to coat the surface of the organic matrix 51 , and also placed in the pores 53 of the organic matrix 51 .
  • the carbonate composite material 5 is higher in strength as compared with the organic matrix 51 alone.
  • the carbonate is deposited in the presence of CO 2 in a state of supercritical fluid (90° C., 30 MPa (300 atm)).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

A pressure container is filled with a base material having at least part of the surface coated with an organic matrix including at least one member selected from the specific functional groups, and a material solution containing a carbonate material as a material for carbonate film and an organic polymer including at least one member selected from the specific groups. In succession, by supplying CO2 into the pressure container at 2 atm or higher, a carbonate film is deposited on the surface of the organic matrix.

Description

    CROSS-REFERENCES TO RELATED APPLICATIONS
  • The present application claims priority under 35 U.S.C. §119 to Japanese Application No.2003-103281, filed Apr. 7,2003, entitled “METHOD OF MANUFACTURING CARBONATE FILM, CARBONATE COMPOSITE MATERIAL, AND METHOD OF MANUFACTURING THE SAME”. The contents of this application are incorporated herein by reference in their entirety.[0001]
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0002]
  • The present invention relates to a method of manufacturing carbonate film capable of manufacturing in a short time, a carbonate composite material excellent in strength, and a method of manufacturing the same. [0003]
  • 2. Description of the Background [0004]
  • Crystals of carbonate such as calcium carbonate have an excellent strength, and are highly expected as high strength material. Further, when combined with wood or other conventional material, carbonate is expected to be used as a composite material excellent in strength. [0005]
  • As crystals of such carbonate, for example, a pearl layer structure of seashell having unique gloss and sufficient strength is known. In this pearl layer structure of seashell, calcium carbonate crystals of uniform thickness of 1 μm or less form a regular layer structure together with biological polymer. By forming such layer structure, the pearl layer structure of seashell has an excellent strength. [0006]
  • It has been difficult, however, to artificially produce such crystals of carbonate created by biological matter of seashell or the like. [0007]
  • In such background, recently, it has been proposed to disperse CaCO[0008] 3 in aqueous solution, circulate CO2 gas, produce CaCO3 saturated aqueous solution from the supernatant, and deposit CaCO3 film on a substrate (see non-patent document 1).
  • [Non-patent document 1][0009]
  • Advanced Materials, Wiley-VCH, Germany, 2002, vol. 14, p. 869 [0010]
  • However, in this conventional method, CaCO[0011] 3-saturated aqueous solution is used. Accordingly, the solubility is small, and reaction quantity is very small. As a result, it takes several days to manufacture CaCO3 film, and since the production quantity is also small, it is hard to manufacture a large area of CaCO3 film.
  • Moreover, it is also difficult in the conventional method to manufacture composite material by combining crystals of carbonate such as calcium carbonate with a conventional material. [0012]
    • SUMMARY OF THE INVENTION
  • The present invention has been made in consideration of such conventional problems, and an object of the present invention is to provide a method of manufacturing carbonate film capable of manufacturing a large area of carbonate film in a short time, a carbonate composite material excellent in strength, and a method of manufacturing the same. [0013]
  • A first aspect of the present invention relates to a method of manufacturing carbonate film comprising the steps of: [0014]
  • filling a pressure container with a base material having at least part of the surface coated with an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and a material solution containing a carbonate material as a material for carbonate film and an organic polymer including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and [0015]
  • supplying CO[0016] 2 into the pressure container at 2 atm or higher to deposit a carbonate film on the surface of the organic matrix.
  • According to the first aspect of the present invention, the base material having at least a part covered with the organic matrix, and the material solution containing carbonate material and organic polymer are processed in the pressure container in the presence of CO[0017] 2 at 2 atm or higher.
  • Therefore, CO[0018] 2 and carbonate material react, and the carbonate is deposited on the surface of the organic matrix on the base material, thereby forming a carbonate film.
  • The carbonate film is estimated to be formed in the following process. [0019]
  • That is, at least one member possessed by the organic matrix selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group mutually act with part of one or more functional groups possessed by the organic polymer selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and at least part of the organic polymer is adsorbed on the surface of the base material. In the organic polymer adsorbed on the surface of the base material, other functional groups than the functional groups adsorbed on the surface of the base material localize cations such as calcium ions contained in the carbonate material at high concentration near the surface of the base material. As a result, crystals are nucleated. In the process of growth of crystals, the organic polymer left over in the solution is adsorbed on the crystals of carbonate and disturbs growth of crystals. As a result, carbonate film is formed. [0020]
  • According to the method of manufacturing the first aspect of the present invention, the carbonate film is formed on the surface of the organic matrix, and a three-layer structure of the base material, organic matrix, and carbonate film is obtained. By selecting a proper material for the base material, it can be used as the base material coated with the carbonate film having unique gloss and high strength. There is exemplified artificial pearl or artificial marble. [0021]
  • After forming the carbonate film, the carbonate film can be peeled from the base material and used. [0022]
  • According to the first aspect of the present invention, the carbonate film is formed in the presence of CO[0023] 2 at 2 atm or higher. Accordingly, the solubility of CO2 dissolved in the material solution is enhanced. As a result, the carbonate film is deposited quickly and the carbonate film can be manufactured promptly. Since the deposition amount of carbonate is large, a carbonate film of a large area can be manufactured.
  • In addition ,the method of manufacturing the first aspect of the present invention uses CO[0024] 2 which is inexpensive, nontoxic, and incombustible. Therefore, the carbonate film can be manufactured at low cost and with high safety.
  • Besides, since CO[0025] 2 is used at high pressure of 2 atm or higher, CO2 rarely leaks to the atmosphere during manufacture of the carbonate film, and global warming can be prevented.
  • According to the first aspect of the present invention, it is available to provide a method of manufacturing carbonate film capable of manufacturing a large area of carbonate film in a short time. [0026]
  • According to the second aspect of the present invention, a carbonate composite material comprises crystals of carbonate, and an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, wherein the crystals of carbonate are disposed on the surface and/or in pores of the organic matrix. [0027]
  • According to the second aspect of the present invention, the carbonate composite material is composed of crystals of the carbonate, and the organic matrix such as wood having a plurality of fine pores on the surface and/or in the inside, and crystals of the carbonate are disposed on the surface and/or in the pores of the organic matrix. Since the crystals of carbonate are very high in strength, the carbonate composite material is very high in strength as compared with the organic matrix alone. [0028]
  • According to the second aspect of the present invention, it is available to provide a carbonate composite material excellent in strength. [0029]
  • According to the third aspect of the present invention, a method of manufacturing carbonate composite material, having crystals of carbonate on the surface and/or in pores of an organic matrix, comprises the steps of: [0030]
  • filling a pressure container with an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and a material solution containing a carbonate material, and [0031]
  • supplying CO[0032] 2 into the pressure container at 2 atm or higher to deposit carbonate film on the surface and/or in pores of the organic matrix.
  • According to the third aspect of the present invention, the organic matrix and the material solution containing carbonate material are processed in the pressure container in the presence of CO[0033] 2 at 2 atm or higher.
  • As a result, the carbonate excellent in strength is deposited on the surface and/or in the pores of the organic matrix. Thus, a carbonate composite material excellent in strength as compared with the organic matrix can be obtained. [0034]
  • The deposition of the carbonate is estimated to proceed as follows. [0035]
  • That is, at least one member possessed by the organic matrix selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group act to localize cations such as calcium ions and/or anions such as carbonic acid ions or hydrocarbon ions contained in the carbonate material at high concentration near the surface of the organic matrix and/or in the pores. As a result, crystals are nucleated, crystals of carbonate grow, and carbonate is deposited. [0036]
  • According to the third aspect of the present invention, the carbonate is deposited in the presence of CO[0037] 2 at 2 atm or higher. Accordingly, the solubility of CO2 dissolved in the material solution is enhanced. As a result, the carbonate is deposited quickly and the carbonate is deposited promptly on the surface and/or in the pores of the organic matrix. Since the deposition amount of carbonate is large, crystals of carbonate are deposited sufficiently on the surface and/or in the pores of the organic matrix.
  • In addition, the method of manufacturing the third aspect of the present invention, same as in the first aspect of the present invention, uses CO[0038] 2 which is inexpensive, nontoxic, and incombustible. Therefore the carbonate composite material can be manufactured at low cost and with high safety.
  • Besides, since CO[0039] 2 is used at high pressure of 2 atm or higher, CO2 rarely leaks to the atmosphere during manufacture of the carbonate film, and global warming can be prevented.
  • Thus, the third aspect of the present invention provides a method of manufacturing carbonate composite material excellent in strength.[0040]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is an explanatory diagram showing a base material of which upper surface is covered with an organic matrix in [0041] embodiment 1 or 2.
  • FIG. 2 is an explanatory diagram showing a carbonate film formed on the surface of organic matrix for covering the base material in [0042] embodiment 1 or 2.
  • FIG. 3 is an explanatory diagram showing a plurality of layers of carbonate film laminated on the surface of organic matrix for covering the base material in [0043] embodiment 2.
  • FIG. 4 is an explanatory diagram showing a general appearance of carbonate composite material in [0044] embodiment 3.
  • FIG. 5 is a sectional view taken in the direction of the arrows substantially along line A-A in FIG. 4. [0045]
  • FIG. 6 is a magnified view of pores having carbonate in carbonate composite material in [0046] embodiment 3.
    • DESCRIPTION OF THE PREFERRED EMBODIMENT
  • In the first aspect of the present invention, as the base material, for example, glass, other ceramics, plastics, metal or wood may be used. [0047]
  • In addition, for the examples of the organic polymer, polyacrylic acid, polyglutamic acid, polyaspartic acid, polyimide, protein, amino acid and derivatives thereof, and related substances may be used. [0048]
  • Moreover, in the first aspect of the present invention and the third aspect of the present invention, CO[0049] 2 is supplied into the pressure container at 2 atm or higher.
  • If the pressure is less than 2 atm, solubility of CO[0050] 2 into the material solution is small. As a result, it takes too much time of manufacture of carbonate film, and it is hard to manufacture a carbonate film of a wide area. At the same time, crystals of carbonate are hardly deposited on the surface and/or in the pores of the organic matrix, and carbonate composite material may not be obtained.
  • At this time, CO[0051] 2 can be introduced into the pressure container in a state of supercritical fluid.
  • In this case, problems possibly occurring when using liquid CO[0052] 2 can be avoided, such as separation or defective dispersion of the material solution and liquid CO2, and a sufficient quantity of CO2 can be supplied quickly near the base material when manufacturing the carbonate film, or on the surface and/or in the pores of the organic matrix when manufacturing carbonate composite material.
  • The supercritical fluid refers to a fluid existing at temperature and pressure above the critical point of an ordinary substance. The fluid in this state is a substance having a dissolving ability equivalent to that of liquid, and diffusibility and viscosity similar to those of gas. [0053]
  • In the first to third aspects of the present invention, usable examples of the organic matrix include aspartic acid, cellulose, chitin, chitosan, wood, polyimide, polyacrylic acid, polyvinyl alcohol, and the like. The organic matrix may be modified with a proper functional group. As the organic matrix, either solid or gel may be used. [0054]
  • In the method of manufacturing the third aspect of the present invention, when gel of arbitrary shape is used as the organic matrix, the portion of water of the gel can be replaced with the carbonate. As a result, a carbonate composite material of complicated shape can be manufactured. [0055]
  • In the first to third aspects of the present invention, as the solvent of the material solution, for example, water, alcohol, fused salt or ionic solution, polar organic solvent or the like may be used. [0056]
  • It is preferable that the carbonate material contain at least one member selected from the group consisting of Ca, Mg, Fe, Cu, Co, Mn, and Ni. [0057]
  • In this case, crystals of carbonate film or carbonate excellent in strength and having unique gloss can be formed. [0058]
  • It is preferable that the carbonate material contain at least one member selected from the group consisting of carboxylate, carbonate, alkoxide, oxide, hydroxide, chloride, nitrate, acetyl acetonate and derivatives thereof. [0059]
  • In this case, reacting quickly with CO[0060] 2, carbonate can be formed.
    • EMBODIMENTS Embodiments 1
  • A embodiment of the first aspect of the present invention is described below. [0061]
  • The method of manufacturing carbonate film in the embodiment, as shown in FIG. 1 and FIG. 2, is characterized by filling a pressure container with a [0062] base material 1 having at least part of the surface coated with an organic matrix 2 including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and a material solution containing a carbonate material as a material for carbonate film 3, and an organic polymer including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group.
  • In succession, by supplying CO[0063] 2 into the pressure container at 2 atm or higher and heating the pressure container, the carbonate film 1 is deposited on the surface of the organic matrix 2.
  • The method of manufacturing the embodiment is specifically described below. [0064]
  • As shown in FIG. 1, in the method of manufacturing the embodiment, first of all, a slide glass was prepared as the [0065] base material 1 coated with a cellulose film as the organic matrix 2. Specifically, 10 g of Cu(OH)2 was dissolved in 100 mL of 25 wt. % NH3 aqueous solution, and 0.3 g of cellulose powder (Nacalai Tesque, Inc.) was added to 30 mL of its supernatant, and a cellulose solution was prepared.
  • The slide glass (27 mm×48 mm) was adhered to a spin coat rotor by a double-side adhesive tape, and the cellulose solution was dropped by dropping pipette, and the rotor was rotated at 390 rpm for 60 seconds to perform spin coating operation. [0066]
  • Then, by impregnating and washing in 200 mL of 0.2N solution of HCl and further washing in ion exchanged water, it was dried for 30 minutes at 105° C. [0067]
  • Thus, as shown in FIG. 1, the base material [0068] 1 (slide glass) having the upper surface coated with cellulose film as the organic matrix 2 was obtained.
  • Then, on the [0069] organic matrix 2, a calcium carbonate film was fabricated as carbonate film. Specifically, as the organic polymer, 0.024 g of polyacrylic acid (molecular weight: 103) was dissolved in 100 mL of ion exchanged water.
  • In succession, a material solution mixing 80 mL of this polyacrylic acid aqueous solution and 2.0 g of calcium acetate as the carbonate material was poured into a beaker of 100 mL together with a base material having the upper surface coated with the organic matrix manufactured above, and it was placed in an autoclave with a capacity of 1000 mL. [0070]
  • In this autoclave, CO[0071] 2 was supplied in a state of supercritical fluid (30 MPa (300 atm), 90° C.), and held for 1 hour in the condition of 90° C. and 30 MPa (300 atm).
  • When taken out from the autoclave, as shown in FIG. 2, a calcium carbonate film was formed as [0072] carbonate film 3. As shown in the drawing, the carbonate film 3 was formed on the organic matrix 2 formed on the upper surface of the substrate 1. The carbonate film 3 was a uniform film with a thickness of 0.6 μm.
  • In this embodiment, the carbonate was deposited in the presence of CO[0073] 2 in a state of supercritical fluid (30 MPa (300 atm), 90° C.).
  • Accordingly, the solubility of CO[0074] 2 dissolved in the material solution is enhanced. As a result, deposition of carbonate film 3 was promptly promoted, and the carbonate film 3 was deposited on the surface of the organic matrix 2 quickly. Besides, since the deposition amount of carbonate film 3 was also increased, the carbonate film 3 was manufactured in a large area.
    • Embodiment 2
  • This embodiment is an example of manufacturing multiple layers by laminating a plurality of layers of carbonate film. [0075]
  • First, same as in [0076] embodiment 1, as shown in FIG. 1, a base material 1 (slide glass) having the upper surface coated with an organic matrix 2 was prepared, and a calcium carbonate film with a thickness of 0.6 μm was formed as carbonate film 3 on the organic matrix 2 of the base material 1. On the base material 1, as shown in FIG. 2, the organic matrix 2 was formed on the upper surface of the base material 1 same as in embodiment 1, and the carbonate film 3 is formed on the organic matrix 2. Thus, sample 1 was obtained.
  • In succession, 0.024 g of polyacrylic acid (molecular weight: 103) was dissolved in 100 mL of ion exchanged water, and 80 mL of this polyacrylic acid aqueous solution and 2.0 g of calcium acetate were poured into a beaker of 100 mL together with this [0077] sample 1, and it was placed in an autoclave with a capacity of 1000 mL. Then, same as in embodiment 1, in this autoclave, CO2 was supplied in a state of supercritical fluid, and held for 1 hour in the condition of 90° C. and 30 MPa, and a carbonate film was formed. This carbonate film was overlaid and formed on the carbonate film of sample 1.
  • By repeating this operation, as shown in FIG. 3, four layers of carbonate film were laminated. As shown in the drawing, the [0078] carbonate films 3 manufactured in this embodiment are laminated in four layers on the organic matrix 2 formed on the upper surface of the substrate 1. The thickness of each carbonate film 3 was 0.6 μm, and the thickness was uniform.
    • Embodiment 3
  • This embodiment is an example of manufacturing a carbonate composite material composed of crystals of carbonate and the organic matrix. [0079]
  • As shown in FIG. 4 and FIG. 5, the [0080] carbonate composite material 5 of the embodiment is a carbonate composite material composed of crystals of carbonate 55, and an organic matrix 51 including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group. As shown in FIG. 4 to FIG. 6, the crystals of the carbonate 55 are disposed on the surface and in pores 53 of the organic matrix 51. FIG. 6 is a magnified view of pores 53 of the carbonate composite material 5 shown in FIG. 5.
  • The [0081] carbonate composite material 5 of the embodiment is cylindrical white lumps as shown in FIG. 4 and FIG. 5. The white lumps of carbonate composite material 5 are composed of crystals of calcium carbonate as carbonate 55 and carboxymethyl cellulose Na (CMC-Na) in gel form as the organic matrix 51. As shown in FIG. 5 and FIG. 6, crystals of the carbonate 55 cover the surface of the organic matrix 51, and are disposed in the pores 53 of the organic matrix 51.
  • Since the crystals of the [0082] carbonate 55 are very high in strength, the carbonate composite material 5 is higher in strength as compared with the organic matrix 51 alone.
  • Then, a method of manufacturing carbonate composite material of the embodiment is explained. [0083]
  • The method of manufacturing the embodiment, as shown in FIG. 4 to FIG. 6, manufactures a [0084] carbonate composite material 5 having crystals of carbonate 55 on the surface and/or in the pores 53 of the organic matrix 51. In the method of manufacturing the embodiment, a pressure container is filled with an organic matrix 51 including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and a material solution containing a carbonate material.
  • In succession, by supplying CO[0085] 2 into the pressure container at 2 atm or higher and heating the pressure container, carbonate is deposited on the surface and/or in pores of the organic matrix.
  • The method of manufacturing the embodiment is more specifically described. [0086]
  • Mixing 4 wt. % aqueous solution of carboxymethyl cellulose Na (CMC-Na) and 240 g of calcium acetate as carbonate material, 50 mL of gel was prepared, and put into a glass cylindrical container with a capacity of 100 mL. This gel (the organic matrix) is composed of skeleton of CMC-Na and a plurality of pores, and the pores are filled with aqueous solution of calcium acetate as the carbonate material. [0087]
  • The glass cylindrical container was placed in an autoclave with a capacity of 1000 mL, and CO[0088] 2 was supplied into the autoclave in a state of supercritical fluid (90° C., 30 MPa (300 atm)), and held for 1 hour in the condition of 90° C. and 30 MPa.
  • When taken out from the autoclave, washing in water and drying, a [0089] carbonate composite material 5 was obtained as shown in FIG. 4 and FIG. 5.
  • In this [0090] carbonate composite material 5, crystals of carbonate 55 excellent in strength are applied to coat the surface of the organic matrix 51, and also placed in the pores 53 of the organic matrix 51.
  • Therefore, the [0091] carbonate composite material 5 is higher in strength as compared with the organic matrix 51 alone.
  • In the method of manufacturing the embodiment, the carbonate is deposited in the presence of CO[0092] 2 in a state of supercritical fluid (90° C., 30 MPa (300 atm)).
  • Therefore, the solubility of CO[0093] 2 dissolved in the material solution is enhanced. As a result, deposition of carbonate was promptly promoted, and the carbonate 55 was deposited on the surface and in the pores 53 of the organic matrix 51 quickly. Besides, since the deposition amount of the carbonate 55 was also increased, crystals of the carbonate 55 was sufficiently deposited on the surface and in the pores 53 of the organic matrix 51.
  • Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described here. [0094]

Claims (12)

What is claimed is:
1. A method of manufacturing carbonate film comprising the steps of:
filling a pressure container with:
a base material having at least part of the surface coated with an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and
a material solution containing a carbonate material as a material for carbonate film and an organic polymer including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and
supplying CO2 into the pressure container at 2 atm or higher to deposit a carbonate film on the surface of the organic matrix.
2. The method of manufacturing carbonate film as claimed in claim 1, wherein the carbonate material contains at least one member selected from the group consisting of Ca, Mg, Fe, Cu, Co, Mn, and Ni.
3. The method of manufacturing carbonate film as claimed in claim 1, wherein the carbonate material contains at least one member selected from the group consisting of carboxylate, carbonate, alkoxide, oxide, hydroxide, chloride, nitrate, acetyl acetonate and derivatives thereof.
4. The method of manufacturing carbonate film as claimed in claim 2, wherein the carbonate material contains at least one member selected from the group consisting of carboxylate, carbonate, alkoxide, oxide, hydroxide, chloride, nitrate, acetyl acetonate and derivatives thereof.
5. A carbonate composite material comprising: crystals of carbonate; and
an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group;
wherein the crystals of carbonate are disposed on the surface and/or in pores of the organic matrix.
6. The carbonate composite material as claimed in claim 5, wherein the carbonate material contains at least one member selected from the group consisting of Ca, Mg, Fe, Cu, Co, Mn, and Ni.
7. The carbonate composite material as claimed in claim 5, wherein the carbonate material contains at least one member selected from the group consisting of carboxylate, carbonate, alkoxide, oxide, hydroxide, chloride, nitrate, acetyl acetonate and derivatives thereof.
8. The carbonate composite material as claimed in claim 6, wherein the carbonate material contains at least one member selected from the group consisting of carboxylate, carbonate, alkoxide, oxide, hydroxide, chloride, nitrate, acetyl acetonate and derivatives thereof.
9. A method of manufacturing carbonate composite material, having crystals of carbonate on the surface and/or in pores of an organic matrix, comprising the steps of:
filling a pressure container with:
an organic matrix including at least one member selected from the group consisting of carboxyl group, amino group, hydroxyl group, phosphonic acid group, phosphoric acid group, ammonium group, trimethyl ammonium group, sulfonic acid group, and sulfuric acid group, and
a material solution containing a carbonate material, and
supplying CO2 into the pressure container at 2 atm or higher to deposit carbonate film on the surface and/or in pores of the organic matrix.
10. The method of manufacturing carbonate composite material as claimed in claim 9, wherein the carbonate material contains at least one member selected from the group consisting of Ca, Mg, Fe, Cu, Co, Mn, and Ni.
11. The method of manufacturing carbonate composite material as claimed in claim 9, wherein the carbonate material contains at least one member selected from the group consisting of carboxylate, carbonate, alkoxide, oxide, hydroxide, chloride, nitrate, acetyl acetonate and derivatives thereof.
12. The method of manufacturing carbonate composite material as claimed in claim 10, wherein the carbonate material contains at least one member selected from the group consisting of carboxylate, carbonate, alkoxide, oxide, hydroxide, chloride, nitrate, acetyl acetonate and derivatives thereof.
US10/817,839 2003-04-07 2004-04-06 Method of manufacturing carbonate film, carbonate composite material, and method of manufacturing the same Expired - Lifetime US7198825B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-103281 2003-04-07
JP2003103281A JP4285051B2 (en) 2003-04-07 2003-04-07 Method for producing carbonate film

Publications (2)

Publication Number Publication Date
US20040197483A1 true US20040197483A1 (en) 2004-10-07
US7198825B2 US7198825B2 (en) 2007-04-03

Family

ID=33095327

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/817,839 Expired - Lifetime US7198825B2 (en) 2003-04-07 2004-04-06 Method of manufacturing carbonate film, carbonate composite material, and method of manufacturing the same

Country Status (2)

Country Link
US (1) US7198825B2 (en)
JP (1) JP4285051B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080085964A1 (en) * 2006-10-06 2008-04-10 Kabushiki Kaisha Toyota Chuo Kenkyusho Solid composite material and production method thereof
CN102796401A (en) * 2012-08-17 2012-11-28 山东宝龙达胶业有限公司 Preparation method of nanometer calcium carbonate with silica-stearic acid composite coating and special for silicone sealant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100587914B1 (en) * 2005-04-19 2006-06-08 한국전력공사 Method for preparing magnesium carbonate by supercritical fluid reaction process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807858A (en) * 1955-08-26 1957-10-01 Argenta Products Co Process of manufacturing synthetic pearl essence
US3706586A (en) * 1970-12-11 1972-12-19 Cities Service Co Method of producing a pearlescent basic lend carbonate pigment
US5007964A (en) * 1988-03-09 1991-04-16 Shiraishi Central Laboratories Co., Ltd. Calcium carbonate, calcium carbonate pigment, process for preparing same, coating composition for information recording paper and information recording paper
US5650562A (en) * 1995-06-07 1997-07-22 Materials Technology, Limited Cement treated with high-pressure CO2
US6093487A (en) * 1994-09-02 2000-07-25 Rhone-Poulenc Chimie Polymer/CaCO3 composite core/sheath particulates and hollow . CaCO.sub3 microbeads prepared therefrom
US20020090462A1 (en) * 2000-11-01 2002-07-11 Ronald Obie Use of carboxymethyl cellulose acetate butyrate as a precoat or size for cellulosic man-made fiber boards

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4435365B2 (en) 2000-03-14 2010-03-17 新日本石油株式会社 Thin film manufacturing method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807858A (en) * 1955-08-26 1957-10-01 Argenta Products Co Process of manufacturing synthetic pearl essence
US3706586A (en) * 1970-12-11 1972-12-19 Cities Service Co Method of producing a pearlescent basic lend carbonate pigment
US5007964A (en) * 1988-03-09 1991-04-16 Shiraishi Central Laboratories Co., Ltd. Calcium carbonate, calcium carbonate pigment, process for preparing same, coating composition for information recording paper and information recording paper
US6093487A (en) * 1994-09-02 2000-07-25 Rhone-Poulenc Chimie Polymer/CaCO3 composite core/sheath particulates and hollow . CaCO.sub3 microbeads prepared therefrom
US5650562A (en) * 1995-06-07 1997-07-22 Materials Technology, Limited Cement treated with high-pressure CO2
US20020090462A1 (en) * 2000-11-01 2002-07-11 Ronald Obie Use of carboxymethyl cellulose acetate butyrate as a precoat or size for cellulosic man-made fiber boards

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080085964A1 (en) * 2006-10-06 2008-04-10 Kabushiki Kaisha Toyota Chuo Kenkyusho Solid composite material and production method thereof
US7858684B2 (en) * 2006-10-06 2010-12-28 Kabushiki Kaisha Toyota Chuo Kenkyusho Solid composite material and production method thereof
CN102796401A (en) * 2012-08-17 2012-11-28 山东宝龙达胶业有限公司 Preparation method of nanometer calcium carbonate with silica-stearic acid composite coating and special for silicone sealant

Also Published As

Publication number Publication date
US7198825B2 (en) 2007-04-03
JP2004307262A (en) 2004-11-04
JP4285051B2 (en) 2009-06-24

Similar Documents

Publication Publication Date Title
Li et al. Polyester nanofiltration membranes for efficient cations separation
Yuan et al. Structure architecture of micro/nanoscale ZIF-L on a 3D printed membrane for a superhydrophobic and underwater superoleophobic surface
Lee et al. Zeolitic imidazolate framework ZIF-8 films by ZnO to ZIF-8 conversion and their usage as seed layers for propylene-selective ZIF-8 membranes
US6112908A (en) Membrane laminates and methods for their preparation
Kim et al. Direct fabrication of free‐standing MOF superstructures with desired shapes by micro‐confined interfacial synthesis
EP2014280B1 (en) Micro-particles, blood-substitute and method for forming same
CN101724841A (en) Method for preparing polymer/silver composite membrane by depositing dopamine
CN102264822A (en) Suspension of cellulose fibers and method for producing the same, film-shaped molded article and method for producing the same
Meng et al. Poly (vinyl alcohol)/sodium alginate polymer membranes as eco‐friendly and biodegradable coatings for slow release fertilizers
WO2016040616A1 (en) Fabrication of metal organic framework materials using a layer-by-layer spin coating approach
US6824716B2 (en) Process for producing porous polymer materials
US7198825B2 (en) Method of manufacturing carbonate film, carbonate composite material, and method of manufacturing the same
CN101791439A (en) Construction method of medical titanium alloy implant surface growth factor delivery system
CN117510956A (en) Coating process of high-barrier film and high-barrier film
Huang et al. Bubble‐Channeling Electrophoresis of Honeycomb‐Like Chitosan Composites
Zoppi et al. Hybrids of poly (ethylene oxide‐b‐amide‐6) and ZrO2 sol–gel: Preparation, characterization, and application in processes of membranes separation
Al‐Ghazzawi et al. Reactive Extrusion Printing for Simultaneous Crystallization‐Deposition of Metal–Organic Framework Films
KR101208909B1 (en) Magnetic Particle and the Fabrication Method Thereof
Bétard et al. Dense and homogeneous coatings of CPO-27-M type metal–organic frameworks on alumina substrates
KR102220488B1 (en) eco friendly vessel for packing food
Strachota et al. Chitosan–oligo (silsesquioxane) blend membranes: Preparation, morphology, and diffusion permeability
US5874374A (en) Method for producing engineered materials from salt/polymer aqueous solutions
US20060068124A1 (en) Method of making an adsorptive membrane
KR101956333B1 (en) Encapsulating composition comprising naphthalene derivatives and coordination metal and method for producing capsule reversibly using the same
KR102193369B1 (en) Semipermeable membrane manufacturing method and semipermeable membrane

Legal Events

Date Code Title Description
AS Assignment

Owner name: KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WAKAYAMA, HIROAKI;FUKUSHIMA, YOSHIAKI;REEL/FRAME:015527/0199;SIGNING DATES FROM 20040319 TO 20040325

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12